CN110400964B - Solid electrolyte membrane for lithium ion battery - Google Patents
Solid electrolyte membrane for lithium ion battery Download PDFInfo
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- CN110400964B CN110400964B CN201910699140.5A CN201910699140A CN110400964B CN 110400964 B CN110400964 B CN 110400964B CN 201910699140 A CN201910699140 A CN 201910699140A CN 110400964 B CN110400964 B CN 110400964B
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- solid electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a solid electrolyte membrane for a lithium ion battery, which comprises a solid electrolyte, an organic polymer and an auxiliary agent, wherein the integral proportion of the solid electrolyte is 5-80%, the proportion of the organic polymer is 20-80%, and the proportion of the auxiliary agent is 0-30%. The invention replaces the traditional polyolefin diaphragm, improves the lithium ion transmission rate and the rate capability of the lithium battery; the solid electrolyte membrane has excellent thermal shrinkage performance at high temperature, and the safety performance of the battery is improved; the solid electrolyte replaces the traditional liquid electrolyte, so that the safety performance of the battery is improved; the organic polymer material in the solid electrode film can bond the positive electrode and the negative electrode in the lithium battery, so that the battery cell is firmer, and the safety of the battery cell in the transportation and use processes is improved.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a solid electrolyte membrane for a lithium ion battery.
Background
Lithium ion batteries are widely used in electronic products such as mobile communication devices, notebook computers, digital cameras and the like due to the characteristics of high energy density, long cycle life, environmental friendliness and the like, and gradually play a role in the fields of electric vehicles and energy storage. At present, the most widely used commercial lithium ion batteries are assembled by using positive and negative electrode plates, liquid electrolyte, polyolefin separators and other materials. The liquid electrolyte is flammable and explosive, and the polyolefin diaphragm is easy to shrink or melt when heated, so that the short-circuit explosion of the battery is easy to cause, and the safety of the lithium ion battery is influenced. The solid electrolyte has the ionic conductivity of the liquid electrolyte and the electronic insulativity of the polyolefin diaphragm, and can replace the liquid electrolyte and the polyolefin diaphragm at the same time, so that the safety performance of the battery is greatly improved. In addition, the solid electrolyte membrane can reduce the short circuit risk caused by lithium dendrite, so that the metal lithium can be used as the negative electrode material of the lithium ion battery, and the energy density of the lithium ion battery is greatly improved. There are three main categories of solid-state electrolyte research currently in use: the electrolyte is an organic polymer electrolyte, an inorganic solid electrolyte and a composite electrolyte formed by compounding an organic polymer and an inorganic solid electrolyte.
The organic polymer electrolyte battery is easy to process, can basically use the existing lithium ion battery technology, but has low room temperature conductivity. The inorganic solid electrolyte has high room-temperature conductivity, but the material cost is high, the battery process is complex, and a plurality of brand new battery production devices need to be developed, so that the cost is further increased. The composite electrolyte membrane has the easy processing performance of an organic polymer electrolyte, and can improve the room temperature conductivity to a certain extent, but has the defects of easy rupture of the membrane due to poor mechanical strength, short circuit of a battery, higher internal resistance of the battery due to poor compatibility with positive and negative electrode interfaces, and poor cycle performance, and the room temperature conductivity needs to be further improved. In view of the above problems, we propose a solid electrolyte membrane for a lithium ion battery herein.
Disclosure of Invention
The invention provides a solid electrolyte membrane for a lithium ion battery, aiming at the technical defects of the existing lithium battery electrolyte membrane such as functionality and the like.
The invention adopts a modified technical scheme to solve the technical defects, and the solid electrolyte membrane for the lithium ion battery comprises a solid electrolyte, an organic polymer and an auxiliary agent, wherein the integral proportion of the solid electrolyte is 5-80%, the proportion of the organic polymer is 20-80%, and the proportion of the auxiliary agent is 0-30%.
As a further preferred mode of the present invention, the solid electrolyte includes: lithium lanthanum titanyl, lithium lanthanum zirconium tantalum oxygen, lithium lanthanum zirconium oxygen, lithium phosphorus oxynitride and a sulfide solid electrolyte of Li3PS 4.
In a further preferred embodiment of the present invention, the organic polymer material is a mixture comprising one or more of polyvinylidene fluoride, polyvinyl fluoride, polyethylene, and polypropylene.
As a further preferred mode of the present invention, the auxiliary agent comprises polymethyl methacrylate plasticizer and lithium salt, and the lithium salt comprises LiTFSI and LiFSI.
As a further preferable mode of the invention, the manufacturing process comprises the following steps:
a. weighing the components according to the proportion of the components of the raw materials and the formula proportion;
b. uniformly mixing the solid electrolyte and the organic polymer material;
and c, adding a certain amount of auxiliary agent, and performing melt extrusion tape casting to prepare a single-layer solid electrolyte membrane with the thickness controlled between 5 and 30 micrometers.
The invention has the following beneficial effects: the lithium ion battery has the advantages that the traditional polyolefin diaphragm is replaced, the lithium ion transmission rate is increased, and the rate capability of the lithium battery is improved; the solid electrolyte membrane has excellent thermal shrinkage performance at high temperature, and the safety performance of the battery is improved; the solid electrolyte replaces the traditional liquid electrolyte, so that the safety performance of the battery is improved; the organic polymer material in the solid electrode plasma membrane can bond the positive electrode and the negative electrode in the lithium battery, so that the battery cell is firmer, and the safety of the battery cell in the transportation and use processes is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a technical scheme that: the solid electrolyte membrane for the lithium ion battery comprises a solid electrolyte, an organic polymer and an auxiliary agent, wherein the whole proportion of the solid electrolyte is set to be 5-80%, the proportion of the organic polymer is set to be 20-80%, and the proportion of the auxiliary agent is set to be 0-30%.
The solid electrolyte includes: lithium lanthanum titanium oxide, lithium lanthanum zirconium tantalum oxide, lithium lanthanum zirconium oxide, lithium phosphorus oxynitride and a sulfide solid electrolyte of Li3PS 4.
The organic polymer material is a mixture composed of one or more of polyvinylidene fluoride, polyvinyl fluoride, polyethylene and polypropylene.
The auxiliary agent comprises polymethyl methacrylate plasticizer and lithium salt, wherein the lithium salt comprises LiTFSI and LiFSI.
In a further preferred embodiment of the present invention, the manufacturing process comprises the following steps:
a. weighing the components according to the proportion of the components of the raw materials and the formula proportion;
b. uniformly mixing the solid electrolyte and the organic polymer material;
and c, adding a certain amount of auxiliary agent, and performing melt extrusion tape casting to prepare the single-layer solid electrolyte membrane, wherein the thickness is controlled to be 5-30 um.
Example 1
The material comprises, by weight, 20 parts of lithium lanthanum titanium oxide, 10 parts of lithium lanthanum zirconium tantalum oxide, 15 parts of lithium lanthanum zirconium oxide, 5 parts of lithium phosphorus oxygen nitrogen, 410 parts of Li3PS, 5 parts of polyvinylidene fluoride, 5 parts of polyvinyl fluoride, 10 parts of polyethylene, 10 parts of polypropylene and 10 parts of polymethyl methacrylate.
Weighing the components according to the proportion of the components of the raw materials and the formula proportion;
then uniformly mixing the solid electrolyte and the organic polymer material;
and finally adding an auxiliary agent, and preparing a single-layer solid electrolyte membrane by melt extrusion tape casting, wherein the thickness is controlled to be 5-30 um.
Example 2
10 parts of lithium lanthanum titanium oxide, 5 parts of lithium lanthanum zirconium tantalum oxide, 15 parts of lithium lanthanum zirconium oxide, 5 parts of lithium phosphorus oxygen nitrogen, 45 parts of Li3PS, 15 parts of polyvinylidene fluoride, 5 parts of polyvinyl fluoride, 10 parts of polyethylene, 10 parts of polypropylene and 20 parts of polymethyl methacrylate.
Weighing the components according to the proportion of the components of the raw materials and the formula proportion;
then uniformly mixing the solid electrolyte and the organic polymer material;
and finally adding an auxiliary agent, and preparing a single-layer solid electrolyte membrane by melt extrusion tape casting, wherein the thickness is controlled to be 5-30 um.
In conclusion, the lithium ion battery provided by the invention replaces the traditional polyolefin diaphragm, the lithium ion transmission rate is increased, and the rate capability of the lithium battery is improved; the solid electrolyte membrane has excellent thermal shrinkage performance at high temperature, and the safety performance of the battery is improved; the solid electrolyte replaces the traditional liquid electrolyte, so that the safety performance of the battery is improved; the organic polymer material in the solid electrode plasma membrane can bond the positive electrode and the negative electrode in the lithium battery, so that the battery cell is firmer, and the safety of the battery cell in the transportation and use processes is improved.
While there have been shown and described what are at present considered to be the basic principles and essential features of the invention and advantages thereof, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (3)
1. A solid electrolyte membrane for a lithium ion battery comprises a solid electrolyte, an organic polymer and an auxiliary agent, and is characterized in that: the integral proportion of the solid electrolyte is set to be 5-80%, the proportion of the organic polymer is set to be 20-80%, and the proportion of the auxiliary agent is set to be 0-30%; the solid electrolyte includes: lithium lanthanum titanium oxide, lithium lanthanum zirconium tantalum oxide, lithium lanthanum zirconium oxide, lithium phosphorus oxynitride and a sulfide solid electrolyte of Li3PS 4; the organic polymer material is a mixture comprising one or more of polyvinylidene fluoride, polyvinyl fluoride, polyethylene and polypropylene; the auxiliary agent comprises polymethyl methacrylate plasticizer and lithium salt.
2. The solid electrolyte membrane for a lithium ion battery according to claim 1, wherein the lithium salt comprises LiTFSI and LiFSI.
3. The process for manufacturing a solid electrolyte membrane for a lithium ion battery according to claim 1, wherein: the manufacturing process comprises the following steps:
a. weighing the components according to the proportion of the components of the raw materials and the formula proportion;
b. uniformly mixing a solid electrolyte with an organic polymer material;
c. then adding an auxiliary agent, and performing melt extrusion tape casting to prepare a single-layer solid electrolyte membrane, wherein the thickness is controlled to be 5-30 um.
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| CN201910699140.5A CN110400964B (en) | 2019-07-31 | 2019-07-31 | Solid electrolyte membrane for lithium ion battery |
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| CN201910699140.5A CN110400964B (en) | 2019-07-31 | 2019-07-31 | Solid electrolyte membrane for lithium ion battery |
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| CN111224150B (en) * | 2019-11-29 | 2022-02-22 | 横店集团东磁股份有限公司 | Solid oxide electrolyte, preparation method thereof and application thereof in lithium ion battery |
| CN113451639A (en) * | 2020-03-25 | 2021-09-28 | 深圳格林德能源集团有限公司 | Solid electrolyte membrane and preparation method thereof |
| CN112768764B (en) * | 2021-01-08 | 2022-06-24 | 上海恩捷新材料科技有限公司 | High-strength solid electrolyte membrane |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108448167A (en) * | 2018-02-08 | 2018-08-24 | 福建猛狮新能源科技有限公司 | A kind of composition polymer solid electrolyte and preparation method thereof |
| CN109768318A (en) * | 2019-03-12 | 2019-05-17 | 浙江锋锂新能源科技有限公司 | A kind of mixing solid-liquid electrolyte lithium battery |
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| KR102562680B1 (en) * | 2016-01-29 | 2023-08-03 | 삼성에스디아이 주식회사 | Polymer electrolyte for lithium secondary battery and lithium secondary battery including the same |
| CN107069082A (en) * | 2017-01-16 | 2017-08-18 | 中南大学 | One kind is saccharide-modified to lead lighium polymer/inorganic hybridization electrolyte and its application |
| CN108365152B (en) * | 2017-12-27 | 2020-09-29 | 清华大学 | Composite diaphragm for lithium battery |
| CN108899579B (en) * | 2018-06-14 | 2021-03-05 | 北京工业大学 | Preparation of self-crosslinking composite solid electrolyte and all-solid-state lithium ion battery formed by same |
| CN109411809A (en) * | 2018-10-18 | 2019-03-01 | 河南电池研究院有限公司 | A kind of preparation method of low temperature flexibility solid polyelectrolyte film and its application in low-temperature solid lithium ion battery |
| CN109627649A (en) * | 2018-12-25 | 2019-04-16 | 苏州顺创新能源科技有限公司 | Photovoltaic polyvinylidene fluoride highly resistance UV transparent fluorine film |
| CN109786812B (en) * | 2019-01-15 | 2021-01-29 | 北京理工大学 | Photocuring solid composite electrolyte and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108448167A (en) * | 2018-02-08 | 2018-08-24 | 福建猛狮新能源科技有限公司 | A kind of composition polymer solid electrolyte and preparation method thereof |
| CN109768318A (en) * | 2019-03-12 | 2019-05-17 | 浙江锋锂新能源科技有限公司 | A kind of mixing solid-liquid electrolyte lithium battery |
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